N-(1-azido-(2,2,2-trihaloethyl) sulfonamides

ABSTRACT

Azides of the formula IN WHICH X is Cl or Br and R is a carboxyacyl, sulfonylacyl or alkoxycarbonyl group. These azides are nematocidal.

I I Umted States Patent [151 3,700,699 Singer Oct. 24, 1972 54] N-(1-AZH)0-(2,2,2-TRIHALOETHYL) [56] References Cited SULFONAMIDES UNITED STATES PATENTS [72] Invent 9' h 3,636,062 1/1972 Singer ..260/349 [73] Assignee: Chevnon Research Company, San

' q Cahf- Primary Examiner-John M. Ford [22] Filed: June 28, 1971 Attorney-A. L. Snow et al.

[21 App1.No.: 163,521 [571- I ABSTRACT Related U.S. Apphcation Data Azides of the formula [62] Division of Ser. No. 789,595, Jan. 7, 1969, Pat.

No. 3,636,062. N;

R-NH-( m-cx, [52] US. Cl ..260/349, 424/226 v "C07c 117/00 in which X is C] or Br and R is a carboxyacyl, sulfonylacyl or alkoxycarbonyl group. These azides are nematocidal.

4 Claims, No Drawings N-(l-AZIDO-(2,2,2-TRIHALOETHYL) SULFONAMIDES CROSS REFERENCE TO RELATED APPLICATIONS This application is a division of copending application Ser. No. 789,595, filed Jan. 7, 1969, now US. Pat. No. 3,636,062.

FIELD OF INVENTION This invention concerns N-(1-azido-2,2,2-

trihaloethyl) amides and carbamates and their use as nematocides.

INVENTION DESCRIPTION wherein X is halogen of atomic number 17 to 35 and R is wherein Z is a chalcogen atom of atomic number 8 to 16 and R is hydrogen, nonarylhydrocarbyl of one to 10 carbon atoms which is free of acetylenic unsaturation, nonarylhalohydrocarbyl which is free of acetylenic unsaturation and of one to 10 carbon atoms and one to three halogen atoms of atomic number 17 to 35, monocarbocyclicaryl of six to 15 carbon atoms, the benzene nucleus of said monocarbocyclicaryl radical being substituted with zero to three alkoxy groups of one to three carbon atoms each, halogens of atomic number 17 to 35 or nitro groups, alkoxy of one to six carbon atoms, phenylthioalkyl in which the alkyl is of one to three carbon atoms and the phenyl is substituted with zero to two halogen atoms of atomic number 17 to 35, phenylsulfonylalkyl in which the alkyl is of one to three carbon atoms and the phenyl is substituted with to 2 halogen atoms of atomic number 17 to 35, or a 5- membered heterocyclic radical of 4 nuclear carbon atoms, one of which is bound to the carbonyl radical of (a), and a single chalcogen heteroatom of atomic number 8 to 16, or

R SO a- (b) wherein R is a nonarylhydrocarbyl radical of one to six carbon atoms which is free of acetylenic unsaturation and is substituted with zero to two halogen atoms of atomic number 17 to 35 or a monocarbocyclicaryl radical of six to 10 carbon atoms in which the benzene nucleus is substituted with zero to two halogens of atomic number 17 to 35, nitro groups or methoxy groups. l-ialogens of atomic number 17 to 35 are chlorine and bromine. Chalcogen atoms of atomic number 8 to 16 are oxygen and sulfur. The term nonaryl as used herein refers to radicals in which a benzene nucleus is not present. Preferably X is chlorine and Z is oxygen in the above formulas.

Particularly preferred compounds represented by the above formula are those in which X is chlorine, Z is oxygen, R is hydrogen, alkyl of one to six carbon atoms, alkoxy of one to three carbon atoms, monoalkenyl of two to five carbon atoms, cycloalkyl of three to six carbon atoms, monocarbocyclicaryl of six to 10 carbon atoms in which the benzene nucleus is substituted with zero to three chlorine atoms, nitro groups or alkoxy groups of one to two carbon atoms each, chloroalkyl of one to six carbon atoms and one tothree chlorine atoms, phenylthiomethyl in which the phenyl group is substituted with zero to two chlorine atoms or phenylsulfonylmethyl wherein the phenyl group is substituted with zero to two chlorine atoms and R is alkyl of 1 to 6 carbon atoms or phenyl substituted with zero to two chlorine atoms.

Hydrocarbyl radicals which R represents in the above formula include alkyl, alkenyl, cycloalkyl and cycloalkenyl radicals. Specific examples of such radicals are methyl, ethyl, isopropyl, butyl, hexyl, heptyl, nonyl, decyl, vinyl, propenyl, bu-tenyl, pentenyl, octenyl, decenyl, cyclopropyl, cyclobutyl, cyclohexyl, cyclooctyl, cyclohexenyl and cyclooctenyl. -Corresponding halohydrocarbyl groups represented by R include chloromethyl, bromomethyl, 2,2-dichloroethyl,

3-bromo-2-chloropropyl, 2-bromoethyl, 5 -ch1oro-2- pentenyl, 6-chlorohexyl, 9-bromodecyl, 4-bromocyclohexyl, 2,4,6-tribromocyclohexyl, 2-ch1orocyclohexenyl and 3-chlorocyclobutyl.

Examples of monocarbocyclic aryl radicals which R may represent are phenyl, tolyl, xylyl, cumyl, p-butylphenyl, p-octylphenyl, 2,4-dibutylphenyl, cinnamyl, benzyl, p-methoxy-phenyl, 2-methoxy-4-tolyl, 2,4,6- tripropoxyphenyl, 2,4,6-tri-nitrophenyl, 3 ,5 dibromophenyl, 2-chloro-4-methoxyphenyl, 2-bromo- 4-tolyl, 2-chloro-4-ethylphenyl, 2,4,6-tribromophenyl, 2,4-di-ethoxybenzyl, 2,4-dinitrophenyl, 2-chloro-5- nitrophenyl and 5-nitro-2-tolyl.

Alkoxy radicals which R may represent include methoxy, ethoxy, isopropoxy, butoxy, isopentoxy and hexoxy.

Heterocyclic radicals which R may represent include 2-furyl, 4-furyl, 5-nitro-2-furyl, 5-chloro-2-furyl, 4-bromo-2-furyl, 3-thienyl, 5-nitro-2-thienyl, 4-chloro- Z-thienyl, 5-bromo-3-thienyl and 2-thienyl.

Phenylthioalkyl groups represented by R are illustrated by phenylthiomethyl, phenylthioethyl, phenylthioisopropyl, 4-chlorophenylthioethyl, 2- chlorophenylthiopropyl, 3,5-dibromophenylthioethyl,

2,4-dichlorophenylthiomethyl and 2-chloro-4- brornophenylthiopropyl.

Phenylsulfonylalkyl radicals represented by R include phenylsulfonylmethyl, phenylsulfonylethyl,

phenylsulfonylisopropyl, 4-chlorophenylsulfonylethyl, 2-chlorophenylsulfony1-propyl, 3,5-dibromophenylsulfonylethyl, 2,4-dichlorophenyl-sulfonylmethyl and 2- chloro-4-bromophenylsulfonylpropyl.

Nonarylhydrocarbyl radicals which R may represent include alkyl, alkenyl and cycloalkyl. Examples of such radicals are methyl, ethyl, propyl, amyl, hexyl, allyl, pentenyl, 2,2-dibromoethyl, chloroallyl, bromobutenyl, cyclopropyl, cyclobutyl, cyclohexyl, 4-chlorocyclohexyl, 2-bromocyclohexyl, 3,5-dicl'ilorocyclohexyl, 3- bromocyclobutyl, chloromethyl, bromoethyl, 2,2- dichloropropyl and 6-chlorohexyl. Aryl radicals represented by R include benzyl, phenyl, tolyl, xylyl, cumyl, 2,4-dinitro-phenyl, 3,5-dimethoxyphenyl, 4-

v dibromo-Z-chloroethyl)-hexanamide,

I clude clude N-( l-azido-2,2,2-trichloroethyl)-2,4-dipropoxybenzamide, N-( l-azido-2,2,2-tribromoethyl)- cyclohexanecarboxamide, N-( l-azido-2,2,2- tribromoethyl)-formamide, N( l-azido-2-bromo-2,2-

N-( l-azido-2,2,2- N-( l-azido-2,2- N-( l-azido-Z- bromo-2,2-dichloroethyl)-4,5-dichlorohexanamide, N- 1-azido-2,2,2-trichloroethyl)-2-bromoacetamide, N 1-azido-2,2,2-trichloroethyl) thiobenzamide, N-( lazido-2,2,2-tribromoethyl)-thioacetamide, N-( l-azido- 2-bromo-2,2-dichloroethyl)-3-bromothiopropionamide, N-( l-azido-2,2,2-trichloroethyl )-thiocyclopropanecarboxamide, N-( l-azido-2,2,2- .trichloroethyl)-4-ethoxybenzamide, N-(l-azido-2,2- dibromo-Z-chloroethyl)-2-chloro-4-bromothiobenzamide, N-( 1-azido-2,2,2-trichloroethyl)-4-bromo3- nitrobenzamide, N-( 1-azido-2,2,2-tribromoethyl)-furamide, N-(1-azido-2,2,2-trichloroethyl-octanamide, N- l-azido-2,2,2-trichloroethyl)-decanamide, N-( lazido-2-bromo-2,2-dichloroethyl)-4-chlorocyclohexanecarboxamide, N-( l-azido-2,2,2-trichloroethyl)-cinnamamide, N-( l-azido-2,2,2-tribromoethyl)-4- bromocinnamamide, N-( l -azido-2,2,2-trichloroethyl S-hexeneamide, N-( l-azido-2,2-dibromo-2- chloroethyl)--chlorofuramide, N-( 1-azido-2,2,2- trichloroethyD- 2-phenylacetamide, N-(1-azido 2,2,2- trichloroethyl)-3-(4-chloro-phenyl)propionamide, N- l-azido-2,2,2-trichloroethyl)-2-( 4-bromo-phenylsulfonyl) acetamide, N-( l-azido-2,2-dibromo-2- chloroethyl )-S-nit rofuramide, .N-( l-azido-2-bromo-2,2 -dichloroethyl)-3-(2,4-dichlorophenylsulfonyl)thiopropionamide, N-( l-azido-2,2,2- trichloroethyl)-2-phenylthio-thioacetamide, N-( lazido-2,2-dibromo-2-chloroethyl)-3-(3,5- dichlorophenylthio)propionamide, N-( l-azido-2,2,2- tribromoethyl)-4-(6-bromo-2-chlorophenylthio)butanamide, N-( l-azido-2,2,2-trichloroethyl)-4-( 3- bromophenylsulfonyl)butanamide, N-(1-azido-2,2,2- tribromoethyl)-4-phenylsulfonylthio-butanamide and N-( 1-azido-2,2-dibromo-2-chloroethyl) 3,S-diethoxv ythiobenzamide.

Sulfonamides represented by the above formula in- N-( 1-azido-2,2,2-trichloroethyl)-4- bromobenzenesulfonamide, N-( 1-azido-2bromo-2,2- dichloroethyl)-3,4-dichlorobenzenesulfonamide, N-( lazido-2,2,2-trichloroethyl)-3,5-dimethoxybenzenesul fonamide, N-( l-azido-2,2,2-trichloroethyl)-3- nitrobenzenesulfonamide, and N-( l-azido-2-bromo-2,2 -dichloroethyl) 2-nitro-4-chlorobenzenesulfonamide, N-( 1-azido-2,2,2-trichloroethyl )-methanesulfonamide, N-( l-azido-2,2,2-tribromoethyl)-ethanesulfonamide, N-( l-azido-2,2,2-tribromoethyl)propenesulfonamide, N-( 1-azido-2-bromo-2,2-dichloroethyl)hexanesulfonamide, N-( l-azido-2,2,2-trichloroethyl)-2,2- dichloroethanesulfonamide, N-( 1-azido-2,2,2- trichloroethyl)-bromobutenesulfonamide, N-(l-azido- 2,2-dibromo-2-chlor oethyl )hexenesulfonamide, N-( 1- azido-2,2,2-tri-chloroethyl)cyclohexanesulfonamide, N-( l-azido-2,2,2-tribromo-ethyl)cyclobutanesulfonamide, N-( l-azido-2,2,2-trichloroethyl)-3,5-dibromodichloroethyl)-thioformamide, trichloroethyl)-3-chlorobutanamide,

cyclohexanesulfonamide, N-( 1-azido-2,2-dibromo-2- chloroethyl)-3-chlorocyclobutanesulfonamide, N-( lazido-2,2,2-trichloroethyl)-4-chlorobutanesulfonamide and N-(1-azido-2,2,2-trichloroethyl)-3-bromo-4- chloropentanesulfonamide.

Carbamates represented by the above-formula include N-(1-azido 2-bromo-2,2-dichloroethyl)-isopropylcarbamate, N-( 1-azido-2,2,2-trichloroethyl)- butylthiocarbamate, N-(1azido-2,2,2-trichloroethyl)- hexylcarbamate, N-( 1-azido-2,2,2-trichloroethyl)- methylthiocarbamate and N-(1-azido-2,2-dibromo-2- chloroethyl)ethylcarbamate.

The azides of this invention are prepared by reacting a corresponding N-(1,2,2,2-tetrahaloethyl) amide with an alkali metal azide. This reaction proceeds according to the following equation:

Cl N 3 wherein R and X are as defined previously and M is an alkali metal such as sodium, potassium and lithium. This reaction will normally be carried out in polar, aprotic solvents such as acetonitrile, dimethoxyethane, tetrahydrofuran, dimethylformamide and dimethylsulfoxide. Normally the N-(1-chloro-2,2,2-trihaloethyl)amide will be dissolved in the solvent to a concentration of about 5 and 20 percent by weight and the solid alkali metal azide will be added with agitation. The temperature of this reaction will usually be in the range of ambient temperature up to about C. -More usually it will be between about 20C. and 60C. Stoichiometric proportions of the reactants will normally be employed. The pressure used in the reaction is not critical. For convenience atmospheric or autogenous pressure may be used. The N-(1-azido-2,2,2-trihaloethyl)amide or carbamate product may be recovered from the reaction mixture by filtering out the alkali metal halide and stripping the solvent from the filtrate.

The organic starting materials for the above reaction may be prepared by the method of British Pat. No. 993,051. In this procedure an amide or a carbamate is condensed with a trihaloacetaldehyde. The resulting hydroxy compound is further reacted with thionyl chloride to replace this hydroxyl group with a chlorine atom. The reaction is as follows: 0H

wherein R and X are as defined previously.

EXAMPLES The following examples illustrate the azides of this invention and their preparation. Unless otherwise indicated, percentages are by weight. 1 EXAMPLE 1 21.1 g. N-( l,2,2,2-tetrachloroethyl) formamide was dissolved in 100 ml. of acetonitrile. 6.5 g. of sodium azide was heated slowly at ambient temperature with stirring. The mixture was stirred overnight, after which the reaction mixture was filtered. The acetonitrile was removed from the filtrate leaving an orange liquid residue. This residue was cooled in an ice bath and the sides of the vessel containing the residue were TABLE I Element analysis, percent 01 S Melting point, Oalcu- Calcu- Compound lated Found lated Found N. 1.azido-2,2,2-trlchlorocthyl)-3,5-dimci.hXybenZBmidc 93-99 30.0 30.35 N-l-nzldo-2,2,2-trlchloroethyl)-3,4,5-trimethoxybenzamide 125-127 27. 8 27. N-(l-uzido-2,2,2-trichloroethyl)-pivalamide 53-57 38.8 38.80 N -(l-nzido-2,2,2-trichloroethyl)-cyclopropanecarboxam 125-127 41. 4 40. 75 N -(l-nzido-2,2,2-trichloroethyl)-2,2-dichloropropronamide 1 37-38 56. 4 52. 35 N-(l-azido-2,2,2-trichloroethy1) -2-phenylsullenylac etamide 87-89 31. 4 31. 35 N-(1-azido-2,2,2-trichloroethy1)-acrylarnide 54-57 41. 4 41. 20 N 1-azido2,2,2-trichloroethyl) Juramlde 94-98 37 6 37. N-( l-azldo-2,2,2-trich1oroethyl)-3 chloropropionami de 78-89 50. 7 49. 05 N -(l-azido-2,2,2-trichloroethyl) -3,4-dichlorobenzam1de. 127-129 49. 0 47. 60 N -(1-azi(lo-2,2,2-trichloroethyl) -4-chloro-3-nitrobenz amide 135-137 38. 05 36. 85

. N -(1-azido-2,2,2-trichloroethyl)-2,4-dichlorobenzam1de.... 81-83 49.0 48.15 N-(1-azido-2,2,2-triehloroethyl)-2-chlorobenzamide 110-116 43.3 42. 30 N-(l-nzido-2,2,2-trichloroethyl)-2-(4-ch1orophenylsulionyl) acetamide- 120-123 35. 0 33. 95 N-(1-azido-2,2,2 trichloroethyl)-2-phenylsullonylacetamlde Liquid 28. 63 28. 95 N-(l-azido-2,2,2 trichloroethyl)-dichloroacetam de 108-110 50.1 58.10 N-(l-azidd2,2,2-trichloroethyl)-2-chloroncetarnide 71.5-72.5 53.4 52. 36 N-(l-azi(lo-2,2,2-trichloroethyl)-2-(4-chl0r0pheny1thio) acetamidm 74-76 37. 98 37. 85 N-(1-azi 1o-2,2,2-trichloroethyl)-isopropylcarbamatc 46. 5-485 38. 65 36.95

1 N=Calculated,17.80%;iound, 16.70%.

2 N=Calculuted, 21.05; found, 21.00; C=Calculated 18.02; found, 17.00.

1 N= Calculated, 20.34; found, 17.75.

ing an oil residuefl'his residue solidified upon standing overnight, giving 9.0 g. N-(l-azido-2,2,2- trichloroethyl)-4-chlorobenzenesulfonamide. This sulfonamide melted at ll2-l16C. Its element analysis was: Calculated: Cl, 39.0%; S, 8.80%; Found: Cl, 37.82%; S, 9.39%.

Other azides of this invention were prepared using the general procedures described above. These azides are tabulated in Table l.

V ,UTIL ILC The azides of this invention exhibit excellent biological activity against nematodes. The nematocidal activity of representative azides of this invention are illustrated by testing them according to the following method.

A 0.38 ml. portion of a 3 percent acetone solution of the test compound was diluted with 1 ml. ac eto ne. The resulting solution was homogeneously mixed with cc. of vermiculite. The treated vermiculite was then mixed homogeneously with 750 g. of soil, dry weight basis, which was severely infested with nematodes 0 this period they were removed and the soil was washed (mixed culture of Meloidogyne javanica and Meloidogyne incognita). This mixing gave a concentration of approximately 15 parts of the test compound per mil-- lion parts of soil. This treated soil was stored for 4 days at 65-75 F. It was then divided equally into 3 parts,

each of which was put into a separate pot and kept for another 3 days-A 3-week old tomato (v. Bonny Best) seedling was then transplanted into each pot and incuk iet .EaPad .s! @qs29a@ne its from their roots. The nematocidal effectiveness of the test compound was determinedby observing each plant for signs of nematode invasion (number of galls formed, stunting, etc.

The results of these tests, reported as the average of the 3 replicates on a 0 to 100 basis 0 indicating no effectiveness; 100 indicating complete effectiveness are reported in Table ll.

TABLE II Nematocidal activity, Compound percent N -(1-azido-2,2,2-trichloroethyl) -3,5-dimethoxybenzamide 100 N -(1-uzido-2,2,2-trlchloroethyl) -3,4,6-trimethoxybenzamlde 100 N -(l-azido-Z,2,2-trlchlorocthyl)-piva1amid 100 N-(1-azldo-2,2,2-trlchloroethyl)-cyclopropane rb 100 N-(1-azldo-2,2,2-trichloroethyl) -2,2-dichloropropionamide 100 N -(1-azido-2,2,2-trichloroethyl)-2-phenylsulienylacetamide 35 N -(1-azldo-2,2,2-tr1chloroethyl) -acrylamide- 100 N -(1-azldo-2,2,2-trichloroethyl) -luramide 100 N-(1-azldo-2,2,Z-trichloroethyl) -3-chloropropionam1de N -(1'-azido-2,2,2-trichloroethyl) -3,4-dichlorobenzamide 03 N -(1-azido-2,2,2-trichloroethyl) -4-chloro-3-nitrobenz amide N -(l-azido-Z,2,2-trlchloroethy1) -2,4-dichlorobenz am1de. 97 N -(1-azido-2,2,2-trichloroethyl) -2-chlorobenzam1de 05 N -(1-azido-2,2,2-trichloroethyl)-2- (4-chlorophenylsulionyl) a aa ki 109 N -(l-azido-2,2,2-trichloroethyl)-2-phenylsulionylacetamide 100 N-(1-azido-2,2,2-trichloroethyl) -2-chloro-5-nitrobenzamidc- 93 N -(1-azldo-2,2,2-trlchloroethyl) -dichloroacetamide 100 N -(l-azido-Z,2,2-trlchloroethy1) -'2-chloroacetamide 100 N -(1-azido-2, 2, Z-trichloroethyl) -2-(4-chlorophenylthio) acetamlde 96 N -(1-azido-2,2,2-trichloroethy1)-isopropylcarbumate 100 N-(l-azido-2,2,2-triehloroethyl)-4-chlorobenzenesulionarnlde 100 As illustrated above, the azides of this invention may be used to control plant-parasitic nematodes by exposing them to a toxic amount of the azide. Thus, these azides will normally be applied to nematode-infested soil at dosages in the range of 3 to 40 lbs. per acre. They may be applied as liquid fonnulations by spraying or injection. They may also be applied as solid formulations containing carriers such assoil sawdust, clay and thelike. When used as a solid, these azides will usually 'be plowed into the soil to facilitate their contact with the nematodes. Following their application to the soil, the soil will be watered to disperse the azide' below 85999511935.-

The above-mentioned liquid formulations will comprise one or more 'azides admixed with-a suitable solvent or diluent. Such formulations may be solutions, dispersions or emulsions. These liquid compositions will also usually contain a surfactant to facilitate the azides penetration intothe soil and generally enhance its effectiveness.

Nematocidai formulations of these azides may also contain stabilizers, spreading agents, fillers, other compatible pesticides and the like.

I claim:

ndvfthsfq u wherein X is halogen of atomic number l7 t o 3 5 wherein R is alkyl, alkenyl, cycloalkyl and cycloalkenyl of one to six carbon atoms and is substituted with zero to two halogen atoms of atomic number 17 to 35; or monocarbocyclic-aryl radical of six to ten carbon atoms in which the benzene nucleus is substituted with zero to two halogens of atomic number 17 to 35, nitr groups or methoxy groups.

2. Compound of claim 1 wherein X is chlorine.

3. Compound of claim 1 wherein R? is alkyl of one to six carbon atoms or phenyl substituted with zero to two chlorine atoms.

4. Compound of claim 1 wherein R is 4-chlorophen- 

2. Compound of claim 1 wherein X is chlorine.
 3. Compound of claim 1 wherein R2 is alkyl of one to six carbon atoms or phenyl substituted with zero to two chlorine atoms.
 4. Compound of claim 1 wherein R2 is 4-chlorophenyl. 